[scandium tris(trimethylsilylmethyl)(THF)2] | 41705-65-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: [scandium tris(trimethylsilylmethyl)(THF)2]
• 英文别名: Sc(CH₂SiMe₃)₃(THF)₂；Methanidyl(trimethyl)silane;oxolane;scandium(3+)
• CAS: 41705-65-1
• 化学式: C₂₀H₄₉O₂ScSi₃
• 分子量: 450.82
• InChiKey: JHVOOJXPFMFWGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.68
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [scandium tris(trimethylsilylmethyl)(THF)2] 以 二氯甲烷-D2 、 氘代苯 、 甲苯 为溶剂， 生成 [Sc(CH2SiMe3)2(THF)(fac-tris(3,5-dimethylpyrazolyl)methane)](B(C6F5)4)
  参考文献：
  名称：

  Synthesis, DFT Studies, and Reactions of Scandium and Yttrium Dialkyl Cations Containing Neutral fac-N₃ and fac-S₃ Donor Ligands

  摘要：

  Reaction of Sc(CH2SiMe3)(3)(THF)(2) with 1,4,7-trithiacyclononane gave Sc([9]aneS(3))(CH2SiMe3)(3), the first organometallic group 3 complex of [9]aneS(3) ([9]aneS(3) = 1,4,7-trithiacyclononane). The corresponding reaction for yttrium gave equilibrium mixtures of Y([9]aneS(3))(CH2SiMe3)(3) and starting materials. Density functional theory (DFT) was used to compare the energies of formation and metal-ligand interaction energies for M([9]aneS(3))R-3 with those for the previously reported fac-N-3 donor complexes M(fac-N-3)R-3 (R = Me or CH2SiMe3; fac-N-3 = 1,4,7-trimethyltriazacyclononane (Me-3[9]aneN(3)) or HC(Me(2)pz)(3)). Reaction of M(CH2SiMe3)(3)(THF)(2) with [NHMe2Ph][BAr4F] (Ar-F = C6F5) in the presence of a facecapping ligand L (L = HC(Me(2)pz)(3), Me-3[9]aneN(3), or [9]aneS(3)) gave the cationic complexes [M(L)(CH2SiMe3)2(THF)](+), which has been structurally characterized for M = Sc and L = [9]aneS3. The corresponding base-free cations [M(L)(CH2SiMe3)(2)](+) were studied by Si-29 NMR spectroscopy and/or DFT and found to possess beta-Si-C agostic alkyl groups in most instances. The isolated cations [Sc(fac-N-3)(CH2SiMe3)(2)(THF)](+) underwent THF substitution reactions with OPPh3 or pyridine, Sc-alkyl migratory insertion with carbodiimides, and C-H bond metathesis with PhCCH. The olefin polymerization capabilities of a series of complexes M(L)R3 have been determined. The scandium complexes were found to be very productive for ethylene polymerization for L (L = HC(Me(2)pz)(3), Me-3[9]aneN(3), or [9]aneS(3) and R = CH2SiMe3 when activated with 1 equiv of [CPh3][BAr4F]. When activated with 2 equiv of [CPh3][BAr4F], the compounds were also very active for the polymerization of 1-hexene.

  DOI：

  10.1021/om800279d
• 作为产物：
  描述：

  trimethylsilylmethyllithium 、 [scandium(III)(chloride)3(tetrahydrofuran)3] 以 四氢呋喃 为溶剂， 生成 [scandium tris(trimethylsilylmethyl)(THF)2]
  参考文献：
  名称：

  阳离子半夹心烷基钪催化异戊二烯和乙烯交替和无规共聚

  摘要：

  钪三烷基配合物 Sc(CH(2)SiMe(3))(3)(THF)(2) 和 1 当量的 Cp'-H 之间的酸碱反应直接提供了相应的单（环戊二烯基）钪二烷基配合物 Cp 'Sc(CH(2)SiMe(3))(2)(THF) (Cp' = C(5)H(5) (1), C(5)MeH(4) (2), C(5) Me(4)H (3)、C(5)Me(5) (4)、C(5)Me(4)SiMe(3) (5)) 的分离产率为 65-80%。具有含杂原子侧臂的类似半夹心配合物 (C(5)Me(4)R)Sc(CH(2)SiMe(3))(2) (R = CH(2)CH(2) PPh(2) (6)、C(6)H(4)OMe-omicron (7)) 是通过 ScCl(3)(THF)(3) 与 1 当量钾的一锅复分解反应获得的配体的盐和 2 当量的 LiCH(2)SiMe(3)。所有的半夹心二烷基配合物 1-7 都对异

  DOI：

  10.1021/ja9056213

文献信息

• Synthesis and Characterization of Heteroscorpionate Rare‐Earth Metal Dialkyl Complexes and Catalysis on MMA Polymerization
  作者：Zhichao Zhang、Dongmei Cui、Alexander A. Trifonov

  DOI：10.1002/ejic.201000108

  日期：2010.6

  rare-earth metal alkyl complexes supported by a heteroscorpionate ligand were prepared and structurally characterized. X-ray diffraction analysis revealed that the heteroscorpionate ligand is face-capping on the rare-earth metal in k(3) mode, making the configuration of the afforded chalky! metal complexes similar to that of half-metallocenes. These complexes are capable of polymerizing methyl methacrylate

  制备了一系列由杂蝎配体支持的稀土金属烷基配合物并对其进行了结构表征。X 射线衍射分析表明，杂蝎酸盐配体在 k(3) 模式下对稀土金属进行了封盖，使所提供的配置变得白垩！金属配合物类似于半茂金属。这些配合物能够聚合甲基丙烯酸甲酯，镥配合物即使在低温下也显示出最高的活性。获得的聚（甲基丙烯酸甲酯）是间规富集的，具有窄的分子量分布。
• 一种三齿稀土金属配合物、制备方法和应用
  申请人：大连理工大学

  公开号：CN111995633B

  公开（公告）日：2021-07-02

  本发明提供了一种三齿稀土金属配合物、制备方法和应用，属于催化技术领域。该三齿稀土金属配合物将含有不同取代基的三齿配体与稀土金属烷基化物直接反应，产率良好。该三齿稀土金属催化剂可直接用于催化环内酯的开环聚合反应，室温下具有较好的催化活性且反应过程可控。
• Chain Transfer to Toluene in Styrene Coordination Polymerization
  作者：Fei Lin、Zhaohe Liu、Meiyan Wang、Bo Liu、Shihui Li、Dongmei Cui

  DOI：10.1002/anie.201914603

  日期：2020.3.9

  The chain-transfer reaction is rather important in coordination polymerization regarding catalytic efficiency, adjustment of molecular weight, and control of chain structure. To date, chain transfer to H2 and Al, Mg, and Zn alkyl compounds and β-H elimination are the commonly encountered modes. Now a novel chain transfer to toluene is reported. By introducing fluorine atoms into the β-diketimine ligands

  链转移反应对于配位聚合在催化效率，分子量调节和链结构控制方面非常重要。迄今为止，链转移至H2和Al，Mg和Zn烷基化合物以及β-H消除是常见的模式。现在报道了一种新颖的向甲苯的链转移。通过将氟原子引入β-二酮亚胺配体，苯乙烯（St）配位聚合的惰性催化体系被转移到高活性体系中。活性随着配体中氟数目的增加而增加。出乎意料的是，尽管有St负载，但所得聚苯乙烯的分子量却非常低（Mn = 2000-6600 Da），每个活性物种最多可得到121条链。通过DFT模拟，MALDI-TOF MS对机理进行了研究，
• Side-Arm Assisted Anilido-Imine Based Rare-Earth Metal Complexes for Isoprene Stereoselective Polymerization
  作者：Yi Wu、Xinli Liu、Dongmei Cui

  DOI：10.3390/molecules26144154

  日期：——

  ligand HL1, smaller scandium based complex 1a and middle size of lutetium based 1b provided lower cis-1,4-selectivity (57.3% and 64.2%), larger yttrium complex 1c displayed high cis-1,4-selectivity (84%). Chelating by crowded HL2, small size of scandium complex 2a provided impressive trans-1,4-selectivity (93.0%), middle lutetium based 2b displayed non-selectivity and larger yttrium complex 2c showed

  苯胺基-亚胺配体o -C 6 H 4 (NHAr 1 )(CH=NAr 2 )，其中 Ar 1是 2,6-二异丙基苄基，Ar 2在邻位上含有氟 (HL 1 ) 或甲氧基 (HL 2 ) -苯基取代基的位置，被合成用于构建基于稀土金属的1a – 1c (HL 1基 Sc, Lu, Y) 和2a – 2c (HL 2基于 Sc, Lu, Y)。根据它们的 NMR 光谱和 X 射线单晶结构，-F 和 -OMe 的侧臂基团被鉴定为与相应的中心金属螯合。通过螯合的杂原子（N，N，F为HL形成的两个平面之间的角度扭曲1和N，N，O为HL 2）中观察到，其中，所述最大的二面角（53.3°）对HL 1 -Y和最小检测到HL 2 -Sc 的二面角 (44.32°) 。这些催化剂经Al i Bu 3和[Ph 3 C][B(C 6 F 5 ) 4 ]活化后，对异戊二烯聚合表现出很大的活性。承载同配体HL 1，较
• Benzylic C–H addition of aromatic amines to alkenes using a scandium catalyst
  作者：Jianhong Su、Yuncong Luo、Xin Xu

  DOI：10.1039/d1cc00306b

  日期：——

  An efficient and selective benzylic C(sp3)–H addition of o-CH3-substituted tertiary aromatic amines to alkenes has been achieved using an anilido-oxazoline ligand supported scandium catalyst, which provides an atom-economic method for the synthesis of a new family of alkylated tertiary anilines. A wide range of amine and alkene substrates are compatible with the catalyst system.

  使用苯胺-恶唑啉配体负载的catalyst催化剂已实现了将邻-CH 3取代的叔芳族胺有效和选择性地用苄基C（sp 3）-H加成烯烃的方法，该催化剂为合成α-烯烃提供了一种原子经济的方法。烷基化叔苯胺的新家族。各种各样的胺和烯烃底物与催化剂体系相容。